Alkylation process and catalyst therefor



United States Patent of Delaware No Drawing. Filed Jan. 24, 1964, Ser.No. 339,895

16 Claims. (Cl. 260--671) This invention relates to a process for theconversion of organic aromatic compounds and more particularly relatesto a process for converting alkylatable aromatic compounds into moreuseful compounds. More specifically, this invention is concerned with aprocess for the alkylation of an alkylatable aromatic compound with anolefinacting compound utilizing a novel catalytic composition of matter.

An object of this invention is to produce alkylated aromatichydrocarbons, and more particularly, to produce monoalkylated benzenehydrocarbons. A specific object of this invention is a process for theproduction of ethylbenzene, a desired chemical intermediate, whichethylbenzene is utilized in large quantities in dehydrogenationprocesses for the manufacture of styrene, one of the starting materialsfor the production of resins and some synthetic rubber. Another specificobject of this invention is to produce alkylated aromatic hydrocarbonsboiling within the gasoline boiling range having high anti-knock valueand which may be used as such or as a component of gasoline suitable foruse in automobile and airplane engines. A further specific object ofthis invention is a process for the production of cumene by the reactionof benzene with propylene in the presence of a novel catalyticcomposition of matter; which cumene product is oxidized in largequantities to form cumene hydroperoxide which is readily decomposed intophenol and acetone. Another object of this invention is to provide aprocess for the introduction of alkyl groups into aromatic hydrocarbonsof high vapor pressure at normal conditions with minimum loss of saidhigh vapor pressure aromatic hydrocarbons and maximum utilizationthereof in the process utilizing a novel catalytic composition ofmatter.

One embodiment of this invention resides in a process for the alkylationof an alkylatable aromatic compound with an olefin-acting compound atalkylation conditions in the presence of a substantially anhydrouscatalyst prepared by combining a phosphoric acid-containing compositewith an oxide of sulfur to effect chemical combination of the phosphoricacid portion of said composite with said oxide of sulfur.

A further embodiment of this invention resides in a process for thealkylation of an alkylatable aromatic compound with an olefin-actingcompound at alkylation conditions in the presence of a substantiallyanhydrous catalyst prepared by combining a phosphoric acid-containingcomposite with an oxide of sulfur selected from the group consisting ofsulfuric acid, sulfurous acid, ammonium oxides of sulfur and metallicoxides of sulfur to effect chemical combination of the phosphoric acidportion of said composite with said oxide of sulfur.

A still further embodiment of this invention is found in a process forthe alkylation of an alkylatable aromatic compound with an olefin-actingcompound at alkylation conditions including a temperature in the rangeof from about 0 to about 300 C. and a pressure in the range of fromabout atmospheric to about 200 atmospheres in the presence of asubstantially anhydrous catalyst prepared by combining a phosphoricacid-containing composite with an oxide of sulfur selected from thegroup consisting of sulfuric acid, sulfurous acid, ammonium oxides ofsulfur and metallic oxides of sulfur to effectchemical combina-3,293,315 Patented Dec. 20, 1966 tion of the phosphoric acid portion ofsaid composite with said oxide of sulfur.

A specific embodiment of the invention resides in a process for thealkylation of benzene with propylene at alkylation conditions includinga temperature in the range of from about 0 to about 300 C. and apressure in the range of from about atmospheric to about 200 atmospheresin the presence of a substantially anhydrous catalyst prepared bycombining a phosphoric acid-containing composite with anoxide of sulfurselected from the group consisting of sulfuric acid, sulfurous acid,ammonium oxides of sulfur and metallic oxides of sulfur to effectchemical combination of the phosphoric acid portion of said compositewith said oxide of sulfur.

A more specific embodiment of the invention resides in a process for thealkylation of benzene with a refinery off-gas at alkylation conditionsincluding a temperature in the range of from about 0 to about 300 C. anda pressure in the range of from about atmospheric to about 200atmospheres in the presence of a substantially anhydrous catalystprepared by combining a phosphoric acid-containing composite with anoxide of sulfur derived from ammonium sulfate to effect chemicalcombination of the phosphoric acid portion of said composite with saidoxide of sulfur.

Other objects and embodiments referring to alternative unsaturatedorganic compounds and to alternative catalytic compositions of matterwill be found in the following further detailed description of theinvention.

It has now been discovered that aromatic compounds and particularlyalkylatable aromatic compounds may be converted to other and more usefulcompounds by contacting said alkylatable aromatic compound with anolefinacting compound in the presence of certain catalytic compositionsof matter which are prepared by specific'methods. Examples ofalkylatable aromatic compounds which may be converted according to theprocess of thisinvention include benzene, toluene, ortho-xylene,meta-xylene, para-xylene, ethylbcnzene, ortho-ethyltoluene,meta-ethyltoluene, para-ethyltoluene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenz'ene, 1,3,5-trimethylbenzene, diethylbenzenes,triethylbenzenes, normal propylbenzene, isopropylbenzene, etc. Preferredalkylatable aromatic compounds are monocyclic aromatic hydrocarbons,that is, benzene hydrocarbons. Higher molecular weight alkyl aromatichydrocarbons are also suitable. These include those aromatichydrocarbons such as are produced by the alkylation of aromatichydrocarbons with olefin polymers and are used as intermediates in thepreparation of sulfonate surface-active agents. Such products arefrequently referred to in the art as detergent alkylate, and includehexylbenzenes, nonylbenzenes, dodecylbenzenes, pentadecylbenzenes,hexyltoluenes, nonyltoluenes, dodecyltoluenes, pentadecyltoluenes, etc.Very often alkylate is obtained as a high boiling fraction in which thealkyl group attached to the aromatic nucleus varies in size from about Cto C Other suitable aromatic hydrocarbons, which at specified alkylationconditions, depending upon the melting point of the aromatic chosen,would be in liquid form, would include those aromatic hydrocarbons withtwo or more aryl groups such as diphenyl, diphenylmethane, triphenyl,triphenylmethane, fluorene, stilbene, etc. Examples of other aromatichydrocarbons utilizable within the scope of this invention which atspecified alkylation conditions, depending upon melting point of thearomatic chosen, would be in liquid form, include those containingcondensed aromatic rings. These include naphthalene, alkyl naphthalenes,anthracene, phenanthrene, naphthacene, rubrene, etc. Of theabove-mentioned aromatic hydrocarbons that could be utilized in theprocess of this invention, the benzene hydrocarbons are preferred, andof the preferred benzene hydrocarbons, ben zene itse f is particularlypreferred.

The olefin-acting compound, acting as the alkylating agent, may beselected from diverse materials including monoolefins, diolefins,polyolefins, actylenic hydrocarbons, and also alcohols, ethers, andesters, the latter including alkyl halides, alkyl sulfates, alkylphosphates, and various esters of carboxylic acids. The preferredolefin-acting compounds are olefinic hydrocarbons which comprisemonoolefins containing one double bond per molecule and polyolefinswhich contain more than one double bond per molecule. Monoolefins whichare utilized as olefinacting compounds in the process of the presentinvention are either normally gaseous or normally liquid and includeethylene, propylene, l-butene, 2-butene, isobutylene, and highermolecular weight normally liquid olefins such as the various pentenes,hexenes, heptenes, octenes, and mixtures thereof, and still highermolecular weight liquid olefins, the latter including various olefinpolymers having from about 9 to 18 carbon atoms per molecule includingpropylene trimer, propylene tetramer, propylene pentamer, etc.Cycloolefins such as cyclopentene, methylcyclopentene, cyclohexene,methylcylohexene, etc. may also be utilized. Also included within thescope of the olefin-acting compound are certain substances capable ofproducing olefinic hydrocarbons or intermediates thereof under theconditions of operation utilized in the process. Typicalolefin-producing substances or olefin-acting compounds capable of useinclude alkyl halides capable of undergoing dehydrohalogenation to formolefinic hydrocarbons and thus containing at least two carbon atoms permolecule. Examples of such alkyl halides include ethyl fluoride,n-propyl fluoride, isopropyl fluoride, n-butyl fluoride, isobutylfluoride, sec-butyl fluoride, tert-butyl fluoride, etc., ethyl chloride,n-propyl chloride, isopropyl chloride, n-butyl chloride, isobutylchloride, sec-butyl chloride, tert-butyl chloride, etc., ethyl bromide,n-propyl bromide, isopropyl bromide, n-butyl bromide, isobutyl bromide,sec-butyl bromide, tert-butyl bromide, etc. As stated hereinabove, otheresters such as alkyl sulfates including ethyl sulfate, propyl sulfate,etc., and alkyl phosphates including ethyl phosphates, etc. may also beutilized. Ethers such as diethyl ether, ethyl propyl ether, dipropylether, etc. are also included within the generally broad scope of theterm olefin-acting compound and may be successfully utilized asalkylating agents in the process of this invention.

In addition, the process of this invention may be successfully appliedto and utilized for complete conversion of olefin hydrocarbons whenthese olefin hydrocarbons are present in minor quantities in various gasstreams. Thus, the normally gaseous olefin for use in the process ofthis invention need not be concentrated. Such normally gaseous olefinhydrocarbons appear in minor quantities in various refinery gas streams,usually diluted with gases such as hydrogen, nitrogen, methane, ethane,propane, etc. These gas streams containing minor quantities of olefinhydrocarbons are obtained in petroleum refineries from various refineryinstallations including thermal cracking units, catalytic crackingunits, thermal reforming units, coking units, polymerization units,dehydrogenation units, etc. Such refinery gas streams have in the pastoften been burned for fuel value, since an economical process for theutilization of their olefin hydrocarbon content has not been available.This is particularly true for refinery gas streams known as offgasstreams containing relatively minor quantities of olefin hydrocarbonssuch as ethylene, propylene, etc.

As hereinbefore set forth, the invention is concerned with a process forthe alkylation of alkylatable aromatic compounds, said process beingeffected in the presence of a catalyst which possesses a high degree ofhydrocarbon conversion activity and is particularly effective as analkylation catalyst for alkylatable aromatic compounds, a representativenumber of which are hereinabove set forth. The catalyst comprises aphosphoric acid-containing composite that is combined with an oxide ofsulfur to effect chemical combination of the phosphoric acid portion ofsaid composite with said oxide of sulfur. The composite, if desired, maycomprise a high surface area solid support although it is one of thefeatures of the catalyst of the present invention that low surface areasupports such as alpha-alumina are satisfactory for the preparation ofcatalysts for use in the process of this invention as contrasted tohydrocarbon conversion catalysts prepared by chemically combining onlyan oxide of sulfur with alpha-alumina, said alpha-alumina in the lattercase being an unsatisfactory support for the oxide of sulfur alone.

As set forth hereinabove, the support may comprise a high surface areasupport. By the term high surface area is meant a surface area measuredby surface adsorption techniques within the range of from about 25 toabout 500 or more square meters per gram and preferably a support havinga surface area of approximately 100 to 300 square meters per gram.However, as set forth hereinbefore, alpha-alumina, which is usuallycharacterized by a surface area ranging from about 10 to about 25 squaremeters per gram is also satisfactory support. Therefore, satisfactorysupports for the preparation of catalysts for use in the process of thisinvention include high surface area crystalline alumina modificationssuch as gamma-, etaand theta-alumina and low surface area supports suchas alpha-alumina although these are not necessarily of equivalentsuitability. In addition to the aforementioned -alpha-, gamma-, etaandtheta-aluminas which may be utilized as solid supports, it is alsocontemplated that other refractory oxides such as silica, zirconia,magnesia, thoria, etc. and combinations of refractory oxides such assilica-alumina, silica-magnesia, alumina-silica-magnesia,alumina-thoria, alumina-zirconia, etc. may also be utilized as solidsupports for the catalyst of the present invention.

As set forth hereinabove, the catalyst comprises a phosphoricacid-containing composite that is combined with an oxide of sulfur toeffect chemical combination of the phosphoric acid portion of saidcomposite with said oxide of sulfur. The phosphoric acid-containingcomposite may be made by combining an acid of phosphorus such as ortho-,py-roor tetra-phosphoric acid with the solid support. Orothophosphoric(H PO and pyrophosphoric acid (H P O find general application due mainlyto the cheapness and to the readiness with which they may be procuredalthough the invention is not restricted to their use, but may employany of the other acids of phosphorus insofar as they are adaptable.However, it is not intended to infer that the different acids orphosphorus which may be employed will produce catalysts which haveidentical effects upon any given organic reactions as each of thecatalysts produced from different acids and by slightly varyingprocedures will exert its own characteristic action.

Triphospho-ric acids, which may be represented by the formula H,-,P Omay also be used as one of the starting materials for the preparation ofthe composite utilized in the catalyst of this invention.

A phosphoric acid mixture which is generally referred to 'aspolyphosphonic acid may also be employed in manufacturing the composite.'Polyphosphoric acid is formed by heating orthophosphoric acid or pyrophosphoric acid or mixtures thereof in suitable equipment such as carbonlined trays heated :by flue gases or other suitable means to produce aphosphoric acid mixture generally analyzing from about 79% to about byweight of P 0 Tetraphosphoric acid, having the general formula H P Owhich corresponds to the double oxide formula 3H O-2P O may beconsidered as the acid resulting when three molecules of Water are lostby four molecules of orthophosphoric acid, H PO The .tetraphosphoricacid may be manufactured by gradual or controlled dehydration or heatingof orthophosphoric acid and pyrophosphoric acid or by adding phosphoruspentoxide to these acids in proper amounts.

The phosphoric acid-containing composite utilized in the presentinvention may contain from about 8% or lower to about 80% by weight ofphosphoric acid and preferably from about 10% to about 50% by weight ofphosphoric acid. Prior art solid phosphoric acid catalytic compositesusually contain from about 50 to about 75% by weight of phosphoric acidcomposited with the solid carrier since lower acid contents cause thesolid phosphoric acid catalytic composite to suffer from a hydrocarbonconversion activity standpoint while those with too high a content ofphosphoric acid have poor structural strength. Solid phosphoric acidcatalytic composites have been manufactured by prior art, methods withfrom about to about 75 by weight of phosphoric acid but compressionpressures ranging from about 5,000 to about 50,000 pounds per squareinch during the manufacturing process have been found necessary to givethe catalyst increased structural strength.

It is therefore a feature of the present invention that the phosphoricacid-containing composite utilized in the present invention may containless than about 50% by weight of phosphoric acid without causing thehydrocarbon conversion activity of the finished catalyst to suffer andwithout the need for subjecting the composite to high compressionpressures during manufacture in order to give the catalyst increasedstructural strength inasmuch as the finished catalyst of the presentinvention prepared as hereinafter set forth has increased structuralstrength and a high degree of stability due to the immobility of thecomponents of the finished catalyst inasmuch as chemical combination ofthe phosphoric acid portion of the composite with the oxide of sulfur isaccomplished as hereinafter described.

Oxides of sulfur which may be chemically bound to the phosphoric acidportion of the phosphoric acid-containing composite include metallicoxides of sulfur in which the metallic portion of the compoundpreferably comprises a metal of Group VI 3 of the periodic table, ametal of the Iron Group of Group VIII, as well as aluminum, etc. such asaluminum sulfate, nickel sulfate, nickel sulfite, chromium sulfate,chromium sulfite, molybdenum sulfate, tungsten sulfate, cobalt sulfate,cobaltous sulfite, ferric sulfate, ferric sulfite, etc. In addition tothe hereinabgove enumerated metallic oxides of suliiur it is alsocontemplated within the scope of this invention that the phosphoricacidacontaining composite may be impregnated with a solution of ammoniumsulfate or ammonum sulfite, or, if so desired, with a solution ofsulfuric or sulfurous acid adiusted to a pH of about 9.0

' by the addition of a sufficient amount of ammonium hydroxide.Following the impregnation, the phosphoric acid-containing support isthen heat treated thereby driving off the ammonia and allowing the oxideof sulfur to remain impregnated on and chemically bonded to thephosphoric acid portion. of the phosphoric acid containing composite.The catalyst comprises an oxide of sulfur chemically combined with thephosphoric acid portion of the composite so as to effect chemicalcombination of the hydroxyl groups of the phosphoric acid with the oxideof sulfur, and as hereinbefore set forth, it is the particularassociation of these components which results in the unusual catalyticproperties of this catalyst. In addition to the aforesaid oxides ofsulfur, the phosphoric acid-containing composite may also be impregnatedwith concentrated sulfuric or suliiurous acid in an amount sufiicientthat the final catalytic composite possesses from about 1 to about 25%by weight of sulfate or sulfite content.

The chemical addition of the oxide of sulfur to the phosphoric acidportion of the phosphoric acid-containing composite will enhance thesurface area characteristics of the composite inasmuch as the finishedcatalytic composite exhibits greater surface area than the phosphoricacid-containing composite orginally possessed. Further, the finalcatalytic composite obtained by the preparation as described hereinaboveis substantially anhydrous due to the chemical combination of the oxideof sulfur with the phosphoric acid-containing portion of the composite.Thus, it is another feature of the present invention that asubstantially anhydrous support initially is not necessary .to preparethe catalyst of the present invention. Still another feature of thepresent invention is that the final catalytic composite does not needhydration during processing as does a phosphoric acid containingcomposite as is taught in the prior art inasmuch as the final catalyticcomposite is substantially anhydrous and thus deterioration of aphysical nature by processing factors tending to further dry thecatalyst is not a problem in the present invention.

As hereinbefore set forth, certain forms of alumina may be utilized assupports for the catalyst of this invention. For example, alumina may beprepared by any of the Well known suitable means of manufacture, oneexample of which is the addition of an alkaline reagent to a salt ofaluminum in an amount sufiicient to form aluminum hydroxide, which, upondrying and calcining, is converted to alumina. Similarly, if the solidsupport comprises both alumina and silica, these components may beprepared by separate, successive or coprecipitate means.

For example, a phosphoric acid-containing composite previously preparedby the methods hereinbefore set forth is then chemically combined withan oxide of sulfur such as by treating the composite with an oxide ofsulfur, said oxide of sulfur being added in an amount suflicient toallow the finished catalytic composite to contain from about 1.0 toabout 25% or more by weight of sulfate or sulfite. Following this, thechemically combined material is then dried by heat treatment in afurnace tube or muflie furnace, etc. The finished catalytic compositecomprising the oxide or sulfur chemically combined with the phosphoricacid portion of the phosphoric acid-conizaining composite is thenutilized as the conversion catayst.

The process of this invention utilizing the catalyst hereinbefore setforth may be effected in any suitable manner and may comprise either abatch or a continuous type operation. The preferred method by which theprocess of this invention may be effected is a continuous typeoperation. One particular method is the fixed bed operation in which thealkylatable aromatic compound and the olefin-acting compound arecontinuously charged to a reaction zone containing a fixed bed of thedesired catalyst, said zone being maintained at the proper operatingconditions of temperature and pressure including a temperature in therange of from about 0 to about 300 C. and preferably in the range offrom about 40 C. to about 180 C., and a pressure in the range of fromabout atmospheric to about 200 atmospheres and at a liquid hourly spacevelocity (the volume of charge per volume of catalyst per hour) in therange of from about 0.1 to about 20 or more, and preferably in a rangeof from 0.1 to about 10, or at a gaseous hourly space velocity in therange of from about to about 1500 or more. The reaction zone maycomprise an unpacked vessel or coil or may be lined with an adsorbentpacking material. The two reactants may be charged through separatelines or, if so desired, may be admixed prior to entry into saidreaction zone and charged thereto in a single stream. This charge passesthrough the catalyst bed in either an upward or downward flow and thealkylated product is continuously withdrawn, separated from the reactoreffluent, and recovered while any unreacted starting materials may berecycled to form a portion of the feed stock. Another continuous typeoperation comprises the moving bed type in which the reactants and thecatalyst bed move either concurrently or counter-currently to each othert while passing through said reaction zone. Yet another continuous typeof operation which may be used is the slurry type in which the catalystis carried into the reaction zone as a slurry in one or the other of thereactants.

Still another type of operation which may be used is the batch typeoperation in which a quantity of the alkylatable aromatic compound, theolefin-acting compound and the catalyst are placed in an appropriateapparatus such as, for example, a rotating or stirred autoclave or analkyl-ation flask. The apparatus is then heated to the desiredtemperature and maintained thereat for a predetermined residence time atthe end of which time the vessel and contents thereof are cooled to roomtemperature and the desired reaction product recovered by conventionalmeans such as for example, by washing, drying, fractional distillation,crystalliaztion, etc.

The following examples are introduced for the purpose of illustrationonly with no intention of unduly limiting the generally broad scope ofthe present invention.

Example I In this example, polyphosphoric acid is treated with ammoniumhydroxide to .a pH of approximately 9.0 and this solution is impregnatedon the solid support, namely gamma-alumina. The impregnated support isthen heated in a furnace tube to a temperature of about 500 C. andmaintained at this temperature for a period of about two hours whileheat treating the composite. During the heat treatment of the compositeto the desired temperature, it will be noted that ammonia gas is evolvedfrom the composite thereby leaving phosphoric acid deposited on therefractory oxide support. This phosphoric acidcontaining compositecontaining approximately 50% by weight of phosphoric acid is thensubjected to chemical reaction at a temperature in the range of fromabout 300 C. to about 600 C. with an oxide of sulfur, namely sulfurtrioxide. The finished catalyst will contain about 8.5 weight percent ofsulfate (which is approximately 2.8 weight percent sulfur). Thiscatalyst is designated as catalyst A. 1 Example II Another catalyst isprepared by impregnating silica with another polyphosphoricacid-ammonium hydroxide solution. The impregnated support is then heattreated in a furnace tube to a temperature of about 500 C. and keptthereat for a period of about two hours. It is noted that ammonia gas isevolved from the composite thereby leaving phosphoric acid deposited onthe refractory oxide support. This phosphoric acid-containing compositecontaining approximately 30% by Weight of phosphoric acid is thensubjected to substantially complete chemical reaction with an oxide ofsulfur derived from sulfuric acid. The composite is subjected to animpregnation with 85 cc. of a solution containing cc. of concentratedsulfuric acid which has been adjusted to a pH of 9.0 with ammoniumhydroxide. The resultant composite is again slowly heat treated in thefurnace tube to about 600 C. and once again the evolution of ammonia gastakes place leaving the oxide of sulfur chemically combined with thephosphoric acid portion of the silica support. This catalyst isdesignated as catalyst B.

Example IIl thereby leaving phosphoric acid deposited on the refractoryoxide support. This phosphoric acid-containing composite containingapproximately 25% by weight of phosphoric acid is then subjected tochemical reaction with an oxide of sulfur derived from aluminum sulfate.The composite is then subjected to an impregnation with a 20% aluminumsulfate solution. The resultant cornposite is again slowly heat treatedin the furnace tube to about 600 C. and chemical combination of theoxide of sulfur and the phosphoric acid portion of the silica supportoccurs. This catalyst is designated as catalyst C.

Example IV In this example, a catalyst is prepared by impregnatingalumina with another polyphosphoric acid-ammonium hydroxide solution.The impregnated support is then heat treated in a furnace tube to atemperature of about 500 C. and kept thereat for a period of about twohours. It is noted that ammonia gas is evolved from the compositethereby leaving phosphoric acid deposited on the refractory oxidesupport. This phosphoric acidcontaining composite containingapproximately 38% by weight of phosphoric acid is then subjected tochemical reaction with an oxide of sulfur derived from ammonium sulfate.The composite is subjected to an impregnation with a 20% ammoniumsulfate solution. The resultant composite is again slowly heat treatedin the furnace tube to' about 600 C. and once again the evolution ofammonia gas takes place leaving the oxide of sulfur chemically combinedwith the phosphoric acid portion of the alumina support. This catalystis designated as catalyst D.

Example V The catalyst prepared according to Example I above anddesignated as catalyst A is utilized in an alkylation reaction todetermine the alkylation activity of said catalyst. In this experiment,grams of the catalyst prepared according to the method of Example I isplaced in an appropriate apparatus which is provided with heating means.In the experiment, benzene and ethylene are charged separately to thealkylation reaction zone. The reactor is maintained at about 500p.s.i.g. and C. Substantially complete conversion of the ethylene isobtained. The product is analyzed for olefins using a mass spectrometerand it is found that the product comprises ethylbenzene, diethylbenzene,polyethylbenzenes and unreacted benzene.

Example VI The catalyst prepared according to Example II and designatedas catalyst B is utilized in the alkylation reaction zone, 100 grams ofthe finished catalyst being placed in the alkylation apparatus. In theexperiment, benzene and ethylene are charged separately to thealkylation zone which is maintained at about 500 p.s.i.g. and 100 C.Based on weight, substantially complete conversion of the ethylene isobtained. The product is analyzed for olefins using a mass spectrometerand it is found that the product comprises ethylbenzene, diethylbenzene,polyethylbenzenes and unreacted benzene.

Example VII Example VIII The catalyst prepared according to Example IVabove and designated as catalyst D is utilized in the alkylation ofbenzene with a synthetic refinery off-gas similar to that normallyobserved from a catalytic cracking unit. A 100 gram batch of thecatalyst is placed in an alkylation reactor and the reactor ismaintained at a temperature in the range of from about 100 C. to about180 C. at a pressure at about 600 p.s.i.g. The composition of thesynthetic off-gas feed is as follows: carbon dioxide, 0.1 mol percent;nitrogen, 29.0 percent; carbon monoxide, 1.3 mol percent; hydrogen, 18.9mol percent; methane, 35.0 mol percent; ethylene, 12.0 mol percent;ethane, 0.5 mol percent; propylene, 2.5 mol percent; propane, 0.1 molpercent; isobutane, 0.1 mol percent; and acetylene, 0.5 mol percent. Theoff-gas and benzene are charged separately to the alkylation zone. Theplant liquid eflluent is tested for unsaturation and is found to have alow bromine index indicating the substantial absence of olefinpolymerization products. The product comprises ethylbenzene,diethylbenzene, polyethylbenzenes, cumene, diisopropylbenzene,polypropylbenzenes and 1,1-diphenylethane.

I claim as my invention:

1. A process for the alk-lation of an alkylatable aromatic hydrocarbonwith an olefin-acting compound at alkylation conditions in the presenceof a substantially anhydrous catalyst comprising a phosphoricacid-containing composite in which the phosphoric acid portion ischemically combined with an oxide of sulfur.

2. A process for the alkylation of an alkylatable aromatic hydrocarbonwith an olefin-acting compound at alkylation conditions in the presenceof a substantially anhydrous catalyst comprising a phosphoricacid-containing composite in which the phosphoric acid portion ischemically combined with an oxide of sulfur selected from the groupconsisting of sulfuric acid, sulfurous acid, ammonium oxides of sulfurand metallic oxides of sulfur.

3. 'A process for the alkylation of an alkylatable aromatic hydrocarbonwith an olefin-acting compound at alkylation conditions including atemperature in the range of from about to about 300 C. and a pressure inthe range of from about atmospheric to about 200 atmospheres in thepresence of a substantially anhydrous catalyst comprising a phosphoricacid-containing composite in which the phosphoric acid portion ischemically combined with an oxide of sulfur selected from the groupconsisting of sulfuric acid, sulfurous acid, ammonium oxides of sulfurand metallic oxides of sulfur.

4. A process for the alkylation of an alkylatable aromatic hydrocarbonwith tan olefin-acting compound at alkylation conditions including atemperature in the range of from about 0 to about 300 C. and a pressurein the range of from about atmospheric to about 200 atmospheres in thepresence of a substantially anhydrous catalyst comprising a phosphoricacid-containing composite in which the phosphoric acid portion ischemically combined with an oxide of sulfur derived from sulfuric acid.

5. A process for the alkylation of an alkylatable aromatic hydrocarbonwith fin. olefin-acting compound at alkylation conditions including atemperature in the range of from about 0 to about 800 C. and a pressurein the range of from about atmospheric to about 200 atmospheres in thepresence of a substantially anhydrous catalyst prepared by combining aphosphoric acid-containing composite with an oxide of sulfur derivedfrom ammonium sulfate to effect chemical'combination of the phosphoricacid portion of said composite with said oxide of sulfur.

6. A process for the alkylation of an alkylatable aromatic hydrocarbonwith an olefin-acting compound at alkylation conditions including atemperature in the range of from about 0 to about 300 C. and a pressurein the range of from about atmospheric to about 200 atmospheres in thepresence of a substantially anhydrous catalyst prepared by combining aphosphoric acid-containing composite with an oxide of sulfur derivedfrom aluminum sulfate to effect chemical combination of the phosphoricacid portion of said composite with said oxide of sulfur.

7. The process of claim 1 further characterized in that said phosphoricacid portion and oxide of acted at a temperature of fro-m about 300 600C.

8. The process of claim 3 further characterized in that said phosphoricacid portion and oxide of sulfur are reacted at a temperature of fromabout 300 C. to about 600 C.

9. The process of claim 3 further characterized in that said alkylatablearomatic hydrocarbon is a benzene hydrocarbon.

10. The process of claim 3 further characterized in that saidolefin-acting compound is an olefinic hydrocarbon.

11. The process of claim 3 further characterized in that saidolefin-acting compound is a normally gaseous olefin.

12. A process for the alkylation of benzene with ethylene at alkylationconditions including a temperature in the range of from about 0 to about300 C. and a pressure in the range of from about atmospheric to about200 atmospheres in the presence ofa substantially anhydrous catalystcomprising a phosphoric acid-containing composite in which thephosphoric acid portion is chemically combined with an oxide of sulfurselected from the group consisting of sulfuric acid, sulf-urous acid,ammonium oxides of sulfur and metallic oxides of sulfur.

13. A process for the alkylation of benzene with propylene at alkylationconditions including a temperature in the range of from about 0 to about300 C. and a pressure in the range of from about atmospheric to about200 atmospheres in the presence of a substantially anhydrous catalystprepared by combining a phosphoric acid-containing composite with anoxide of sulfur derived from aluminum sulfate to effect chemicalcombination of the phosphoric acid portion of said composite with saidoxide of sulfur.

14. A process for the alklation of benzene with butylene at alkylationconditions including a temperature in the range of from about 0 to about300 C. and a pressure in the range of from about atmospheric to about200 atmospheres in the presence of a substantially anhydrous catalystprepared by combining a phosphoric acid-containing composite with anoxide of sulfur derived from ammonium sulfate to effect chemicalcombination of the phosphoric acid portion of said composite with saidoxide of sulfur.

15. A process for the alkylation of benzene with a refinery off-gas atalkylation conditions including a temperature in the range of from about0 to about 300 C. and a pressure in the range of from about atmosphericto about 200 atmospheres in the presence of a substantially anhydrouscatalyst prepared by combining a phosphoric acid-containing compositewith an oxide of sulfur derived from ammonium sulfate to effect chemicalcombination of the phosphoric acid portion of said composite with saidoxide of sulfur.

16. A process for the alkylation of benzene with ethylene at alkylationconditions including a temperature in the range of from about 0 to about300 C. and a pressure in the range of from about atmospheric to about200 atmospheres in the presence of a substantially anhydrous catalystcomprising a phosphoric acid-containing composite in which thephosphoric acid portion is chemically corriibined with an oxide ofsulfur derived from sulfuric aci sulfur are re- C. to about ReferencesCited by the Examiner UNITED STATES PATENTS 2,843,640 7/1958 Langlois etal 252-437 X DELBERT E. GANTZ, Primary Examiner.

C. R. DAVIS, Assistant Examiner.

1. A PROCESS FOR THE ALKALATION OF AN ALKYLTABLE AROMATIC HYDROCARBONWITH AN OLEFIN-ACTING COMPOUND AT ALKYLATION CONDITIONS IN THE PRESENCEOF A SUBSTANTIALLY ANHYDROUS CATALYST COMPRISING A PHOSPHORICACID-CONTAINING COMPOSITE IN WHICH THE PHOSPHORIC ACID PORTION ISCHEMICALLY COMBINED WITH AN OXIDE OF SULFUR.